Indian J ournal of Chemical Technology

Vol. 12, March 2005, pp. 232-243

Catalytic Hydrogenation
J aime Wisniak*
Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel 84105

Development of catalytic hydrogenation is one of the most significant chapters in theoretical and applied chemistry,
which led to the opening of a whole series of new industries, particularly in the petrochemical area. The mechanism for a
catalytic reaction involving the presence of an intermediate complex formed by the catalysts and one of the reagents, which
eventually led to our present understanding of the phenomenon was suggested by Paul Sabatier. For his achievements in the
development of catalytic processes Sabatier was awarded the 1912 Nobel Prize of chemistry, together with Victor Grignard.
Catalytic hydrogenationa new technique, was con-
tributed to science, by Paul Sabatier (1854-1941). The
basic work of P Sabatier in this fundamental scientific
and industrial subject forms the basis of our modern
theories about catalysis and catalysts, as well as of the
processes for the thermal and catalytic cracking of the
heavy fractions of petroleum, isomerisation and po-
lymerization of hydrocarbons, hydroforming, synthe-
sis of ammonia, methane, methanol, a very large
number of intermediates and fine chemicals, hydro-
genation of liquid fats, dye intermediates, and the
Fischer-Tropsch process for the manufacture of syn-
thetic fuels.
Here, first the work of P Sabatier that led to the
discovery of catalytic hydrogenation and the postula-
tion of a mechanism for heterogeneous reactions, is
being described and then some details about the life
and career of P Sabatier, that will shed light on the
road that led him to the Nobel Prize is being given.

Inorganic chemistry
During his doctoral thesis Sabatier prepared so-
dium monosulphide (Na
2
S) anhydrous and hydrosul-
phides in the pure state (NaSH, NaSH.2H
2
0,
NaSH.3H
2
O); he established the formula of a hy-
drated potassium hydrosulphide and showed that a
number of alkaline polysulphides that had been de-
scribed as definite chemical species were actually
mixtures containing free sulphur. He developed an
original method for the preparation of the sulphides of
calcium, barium, and strontium in the pure state based
on passing a stream of hydrogen over the correspond-
ing carbonates heated to live red (about 500C). He
described for the first time a method for the prepara-
tion of aluminum sulphide pure and crystallized, by
reacting hydrogen sulphide with alumina heated to the
temperature of red in a carbon boat
3
.
After moving to Toulouse he continued his studies
of sulphur and sulphides. Carl Wilhelm Scheele
(1742-1786) had shown in 1777 that alkaline and al-
kaline-earth polysulphides treated with a diluted acid
did not liberate hydrogen sulphide, like they did with
the corresponding sulphides, but generated an oily
liquid having an unpleasant smell, from which no
compound of definite composition could be separated.
Berthollet
4
and Louis-J acques Thnard (1777-
1857)
5,6
, among others, had tried to determine the
composition of this substance that seemed to be com-
posed by a mixture of hydrogen polysulphides, ac-
companied by hydrogen sulphide and sulphur, but the
analysis of these products had proven very difficult
because they decomposed easily in contact with many
substances, particularly glass. Sabatier solved the
problem by distilling the oil under vacuum and isolat-
ing a liquid having a composition very close to hy-
drogen disulphide, H
2
S
2
, which he named persulphure
dhydrogne (hydrogen persulphide). The errors in
relation to the theoretical composition were due to the
presence of a small amount of dissolved sulphur. Sa-
batier studied the properties of the persulphide, in par-
ticular its ability to decompose violently under the
action of light or the presence of substances that re-
acted with it forming unstable combinations (eg, wa-
ter, alcohols, ethers and alkaline sulphides). In the
presence of water it formed a rather unstable form of
amorphous sulphur, insoluble in carbon disulphide,
while the action of ether led to the formation of crys-
talline variety of sulphur known as soufre nacre (pearl
sulphur) or soufre de Gerne
3
.

*E-mail: wisniak@bgumail.bgu.ac.il
EDUCATOR


233
Afterwards, he developed a new preparation
method for silicon disulphide SiS
2
, which had been
synthetised before by Frmy: Treatment of crystalline
silicon heated to red with hydrogen sulphide. He
found the concurrent transport of amorphous and
crystalline silicon, observation that led him to assume
the simultaneous formation of a sublimable sub-
sulphide of silicon, SiS, stable only at high tempera-
ture, and decomposing slowly on cooling. In fact,
rapid cooling of the vapours generated by the reaction
allowed him to isolate this metastable sub-sulphide at
room temperature and study its properties
3
.
By reacting hydrogen sulphide with boron at the
red temperature he was able to develop a new method
of preparation of boron sulphide, B
2
S
3
, which he iso-
lated in two amorphous forms, one white and opaque,
the other transparent and vitreous, and in a crystalline
form obtained by sublimation at 200C of the white
amorphous sulphide. The formation of a volatile bo-
ron sulphide was accompanied by that of sub-
sulphide, to which Sabatier assigned the formula B
4
S,
and that of a hydrosulphide of probable composition
B(SH)
3
. He also obtained the sub-sulphide by the ac-
tion of hydrogen at red temperature on the normal
sulphide, and described its properties and its com-
pounds
3
.
He then went on to study selenides, He isolated for
the first time a silicon selenide, SiSe
2
, having a metal-
lic aspect, unstable under the action of water, and a
yellow boron selenide, B
2
Se
3
, sublimable, and de-
stroyed by water. In addition, he recognized the for-
mation of a sub-selenide of boron, non-volatile
3
.
From 1881 onwards he studied different hydrates
of metallic chlorides, determining their heats of hy-
dration, stability, the possibility of their dehydration
under cold, and their reaction with cold concentrated
hydrogen chloride. In particular, he studied the hy-
drates of ferric chloride and cupric chloride and the
conditions for their formation and dehydration. He
showed that the absorption of hydrogen chloride by a
solution of cupric chloride decreased the solubility of
this salt yielding crystals of hydrated cupric chloride
that dissolved under the action of an additional
amount of hydrogen chloride, leading to the formation
of complex hydrochlorides. Sabatier was one of the
first to use spectroscopy of absorption to study hy-
drates, particularly those of cupric bromide
7
. Led by
the indications of the absorption spectra of solutions
of cupric bromide in hydrogen bromide, he succeeded
in isolating a complex bromhydrate, which crystal-
lized into black crystals. His discoveries in this sub-
ject led to the development of the technique for de-
tecting cupric compounds in the presence of hydrogen
bromide: they yield a purple coloration, easily ob-
servable and having a characteristic wave length in
the visible absorption spectra
3
.
In 1896, he observed that the reaction of all copper
compounds with a nitro sulphuric solution (nitrosul-
phuric acid), obtained by dissolving nitric acid in sul-
phuric acid, yielded an intense blue purple solution
due to the reduction of the nitric acid to a new acid,
which he named nitrosodisulphonic acid (today: nitro-
sisulphonic acid). By studying the absorption spectra
he established that the colouration was not due to the
copper but corresponded to the new acid formed. He
also found that this reduction could be obtained with
the help of other metallic reducing agents or with or-
ganic substances. He then proceeded to the direct syn-
thesis of nitrosisulphonic dark blue, by the reaction
between nitric oxide, oxygen, and sulphur dioxide, in
the presence of a small amount of water. He proved
that nitrosisulphonic acid could produce several me-
tallic salts, particularly a blue cupric salt and a pink
ferric salt
3
.

Heterogeneous reactions
What makes Sabatiers discoveries even more sen-
sational is the simplicity of the equipment he built for
his studies of heterogeneous reactions: The reactor
consisted of a glass tube filled with catalyst and con-
nected to a oxygen generator, a mechanism for adding
the reagents, and a receptacle for collecting the reac-
tion products. The hydrogen generator, developed by
Deville, operated continuously, and was based on the
reaction between diluted hydrogen chloride over
granulated zinc. The hydrogen generated was washed
by passing it through caustic soda, sulphuric acid, and
through tubes filled with copper turnings heated to
about 500C. The reaction tube had a diameter of 14-
18 mm and length 60 to 100 cm and was positioned
within a bed of fine sand to assure constant tempera-
ture. The reactor was heated by either a gas burner or
an electrical heater
8
.
In 1890 Mond, Langer, and Quincke announced
that by the direct action of carbon monoxide on very
finely divided nickel, prepared by the reduction from
its oxide, they had obtained nickel carbonyl, Ni(CO)
4
,
a volatile compound resulting from the fixation of CO
on the metal. They also reported that reduced iron
yielded a similar compound
9
. Their procedure was
INDIAN J . CHEM. TECHNOL., MARCH 2005


234
very simple: It involved passing a current of CO over
finely divided metallic nickel at a temperature be-
tween 350 and 450C, yielding CO
2
gas and a solid
mixture of a black amorphous powder of nickel and
carbon. The composition of the powder varied widely
with the temperature employed and still more with the
time the reaction was carried on. In this manner they
obtained a product containing as much as 85 mass
percent of carbon and 15% nickel. When a finely di-
vided nickel was obtained, for example, by reducing
nickel oxide by hydrogen at about 400C was allowed
to cool in a slow current of carbon monoxide, the gas
was readily absorbed as soon as the temperature de-
scended to about 100C. If the current of CO was con-
tinued or was replaced by one of inert gases (such as
carbon dioxide, nitrogen, hydrogen, or even air), a
mixture of gases was obtained which contained up-
wards of 30% mass of nickel-carbon oxide. Analysis
of the gas indicated that it corresponded to the for-
mula Ni(CO)
4
.
After Berthelot and Mond in 1891, independently,
had also succeeded in making iron carbonyl,
Fe(CO)
5
10,11
, Sabatier and his doctoral student Ser-
endens speculated about the possibility that other un-
saturated gaseous molecules such as nitric oxide, ni-
trous oxide, nitrogen peroxide, acetylene, and ethyl-
ene could also be fixed on nickel or on reduced iron,
giving well-defined, stable, and volatile products
comparable to nickel carbonyl. They first tried unsuc-
cessfully to fix nitric oxide (NO) on nickel, cobalt,
iron, and copper; at high temperatures nitric oxide
was reduced to nitrogen, with formation of NiO, CoO,
FeO, and CuO. Similar results were obtained with
N
2
O, but when passing vapours of NO
2
over copper
freshly reduced from its oxide, they observed that at
room temperature (25 to 30C) there was a regular
fixation leading to a definite compound, solid, black,
unstable, and nonvolatile, of nitrated copper, Cu
2
NO
2.

In all cases, the experimental technique involved re-
ducing with a current of hydrogen the finely divided
metal oxide placed inside a heated glass tube and then
passing the unsaturated gas through the tube. Sabatier
and Senderens made a detailed study of the properties
of the new compound: It was not altered by dry, cold
air, but when heated in the presence of pure dry nitro-
gen, it decomposed at about 90C releasing NO
2
, NO,
and N
2
. Carrying the reaction in a Faraday tube (a
closed bent tube cooled at one end) it was possible to
obtain liquid NO
2
. Nitrated copper was decomposed
violently by water (or humid air) with release of NO;
it was not decomposed by cold hydrogen but on heat-
ing to about 180C, it generated ammonia and ammo-
nium nitrite. Reduced cobalt, reduced nickel, and re-
duced iron gave similar reactions, but the products
were less stable
12-15
.
Sabatier and Senderens decided now to repeat their
experiments, this time with ethylene and acetylene.
Then, in 1896 they learned that Moissan and Moureu
had recently tried the fixation of acetylene on the
same metals
16
. They had passed a current of acetylene
on slivers of iron, nickel, or cobalt freshly reduced
from their oxides by hydrogen and chilled in this gas,
and observed a brilliant incandescence. The high tem-
perature thus produced decomposed the greater part of
the acetylene into hydrogen and a large amount of
carbon, which would eventually block the tube. The
remaining acetylene was converted into liquid hydro-
carbons (such as benzene and styrene), which closely
resembled those obtained by Berthelot by heating
acetylene to dull redness inside a bell inverted over
mercury. According to Moissan and Moureu cette
reaction est due un phnomne physique (this reac-
tions is due to a physical effect): reduced iron, nickel,
or cobalt being extremely porous, absorbed the acety-
lene with production of enough heat to cause its spon-
taneous destruction. The reaction being endothermic,
incandescence was reached and maintained as long as
the acetylene entered. The incandescence also deter-
mined the polymerization of the acetylene into liquid
products. However, Moissan and Moureu neglected to
analyze the free gas, which they judged to consist of
hydrogen, and examined the liquids only sufficiently
to recognize the presence of benzene. Similar results
were obtained with platinum black
12
.
Sabatier made some discreet inquiries whether
Moissan and Moureu would be continuing these ex-
periments, and after learning they would not, he and
Senderens repeated the experiments but using ethyl-
ene instead of acetylene, a hydrocarbon less violent in
its reactions. The procedure the followed was similar
to the one used before: They directed a current of eth-
ylene upon slivers of reduced nickel and noticed that
this time no reaction occurred at room temperature.
Raising the temperature progressively, a brilliant in-
candescence of the metal took place at about 300C,
which disappeared in a voluminous deposit of black
carbon, proving the destruction of ethylene. At around
300C they, too, observed a blockage of the tube con-
taining finely divided nickel, and the production of
free hydrogen. The gases released did not react
EDUCATOR


235
significantly with an aqueous solution of bromine or
with an ammonia solution of cupric chloride, which
showed that they did not contain measurable amounts
of ethylenic or acetylenic hydrocarbons. But they also
found methane to be almost pure. Sabatier and
Senderens concluded that an unstable combination
between nickel and ethylene had formed, analogous to
nickel carbonyl, which doubled itself into carbon,
methane, and nickel, C
2
H
4
C +CH
4
, which could
then repeat an identical process
17
. Pursuing this idea,
the two tried the reduction of the finely divided nickel
oxide at temperatures below 300C, cooling the re-
duced nickel first in a current of hydrogen and then of
ethylene. After washing the gases leaving the reactor
with bromine to absorb any traces of ethylene, they
discovered that is was a mixture of ethane, formne (a
mixture of equal volumes of ethane and hydrogen),
and hydrogen, with traces of hydrocarbons. Raising
the temperature above 325C decomposed the ethane
into methane and carbon and the formne into carbon
and free hydrogen. The overall ratio between ethane
and hydrogen formed varied with temperature, at
325C it was 75% by volume ethane and 25% hydro-
gen and at around 390C it was essentially pure for-
mene. Hydrogen could only be formed from hydro-
genation of ethylene, and this hydrogenation had been
provoked by the presence of nickel. In other words, it
seemed that reduced nickel had the property of hy-
drogenating ethylene. To test this possibility they re-
peated their experiments, this time directing a mixture
of equal volumes of ethylene and hydrogen upon a
bundle of thin slivers of freshly reduced nickel,
slightly heated at temperatures from 30 to 40C. A
considerable increase in temperature was observed.
The results confirmed their expectations: only one
half of the volume of practically pure ethane was ob-
tained, and the reaction continued indefinitely without
the necessity of heating and without an appreciable
modification of the metal. At a higher temperature
(150 to 180C) the reaction was still very rapid and a
catalyst bed of a few centimeters of metallic slivers
was sufficient to accomplish it
12
. This result, they be-
lieved, doit tre certainment attribue la formation
temporaire dune combinaison directe et spcifique du
nickel et de lthylne (ought certainly to be attrib-
uted to the temporary formation of a direct and spe-
cific combination of nickel and ethylene)
18
. Cobalt,
iron, copper, and platinum black gave similar but less
intense results. It was not only the easy hydrogenation
of ethylene and acetylene that was extraordinary in
their results, but also the use of metals outside the
platinum family for catalysts. This result was com-
pletely unexpected
19
.
The following year Sabatier and Senderens discov-
ered that nickel is also capable of hydrogenating
acetylene, but that reaction could be initiated at room
temperature
20
. Acetylene was first hydrogenated to
ethylene and then to ethane, depending on if the react-
ing mixtures contained the same or double the volume
of hydrogen. The reaction was very exothermic and
the temperature within the reactor could reach 100 to
150C, depending on the length of the tube. Again,
reduced cobalt, iron, and copper, as well as finely di-
vided platinum sponge or black, slightly heated, led to
an analogous but less energetic reaction. With freshly
reduced copper, for example, the composition of the
exiting gas varied with the temperature; at about
130C, it contained 11% volume of ethylene and
178% ethane, and at 150C, 331% ethylene, 20% eth-
ane, and 184% of higher unsaturated hydrocarbons
21
.
Further work examined in more detail the hydro-
genation of ethylene and acetylene using other met-
als
22,23
.
After having studied in depth the hydrogenation of
unsaturated hydrocarbons Sabatier and Senderens
turned to the next challenging problem: Hydrogena-
tion of benzene. This reaction had been attempted by
Berthelot using his universal agent of hydrogenation,
a concentrated solution of hydrogen iodide in a sealed
tube heated to 250C (under these conditions hydro-
gen iodide decomposes into hydrogen and iodine), but
instead of cyclohexane, which boils at 81C, he had
only obtained its isomer, methylcyclopentane, which
boils at 69C. Instead, Sabatier and Senderens tested
the possibility of using reduced nickel and excess hy-
drogen at 200C. The gaseous mixture issuing from
the reactor was sent to a U-tube surrounded by ice,
within which the vapours of cyclohexane were ex-
pected to condense to a liquid product. After boiling
the benzene for a rather short time, they noticed that
the tube became clogged by colourless crystals, which
they assumed to be benzene, solidifying at 4C,
whereas cyclohexane was reported in the literature to
crystallize at 11C. On opening the U-tube they de-
tected, instead of the odour of the original benzene,
the special intermediate odour between that of chloro-
form and that of rose, which belongs to cyclohexane:
It was from cyclohexane obtained practically pure at
the first attempt, the fusion of which is in reality
65Cthat hour was one of the greatest joy in my
INDIAN J . CHEM. TECHNOL., MARCH 2005


236
life. The transformation of benzene had been com-
plete
14,24
.
In the following three years, Sabatier and Sender-
ens hydrogenated unsaturated ethylenic or acetylenic
carbides into saturated carbides, nitro compounds and
nitriles into amines, aldehydes and ketones into the
corresponding alcohols, unsaturated hydrocarbons of
cyclic nuclei, homologous with benzene (polyphenyls,
naphthalene, anthracene, etc) into the corresponding
saturated hydrocarbons, the phenols into the cyclo-
hexanic alcohols, and aniline into cylohexylamine.
They also found that they could produce the major
types of natural petroleum by modifying conditions of
the hydrogenation of ethylene
1,14
. They also realized
the synthesis of methane by hydrogenating carbon
dioxide or carbon monoxide
25,26
.
With Mailhe, another doctoral student, Sabatier
found that some metal oxides were catalysts not for
hydrogenation and dehydrogenation, but instead for
hydration and dehydration. While ordinary alcohols
directed at 250C on reduced copper split into hydro-
gen and aldehyde, the same vapour directed on fine
alumina or thoria split into water and aldehyde
27,28
.
They also observed that amorphous oxides were more
active catalysts for dehydrogenation or dehydration
than the crystalline oxides ones
28,29
. Calcination of the
latter at temperatures higher than 500C led to a nota-
ble agglomeration. The calcinations reduced the ac-
tive surface by modifying the nature and distribution
of the active centers. This was the first example of the
sintering effects, which were later used to graduate
the activity of catalysts.

Catalysis
Catalysis is a phenomenon known from very an-
cient times, although not its theory or characteristics.
By the nineteenth century, enough experimental in-
formation began to accumulate to call the attention of
scientists. In 1811, Sigismund Constantin Kirchhoff
(1764-1833) discovered that mineral acids upon heat-
ing changed starch into dextrin and sugar, without
themselves being modified by the reaction
30
. In 1833
Anselme Payen (1795-1871) and J ean-Franois Per-
soz (1805-1868)
31
found that the transformation of
starch discovered by Kirchhoff was attributable to the
action of a special substance, which they called dia-
stase (amylase), which can be extracted from germi-
nated barley by water and purified by repeated pre-
cipitation with ethyl alcohol; they had also found that
the activity is eliminated by heating to 100C. Payen
and Persoz studied in detail the transformation of
starch into dextrin and then into sugar by the action of
diastase and proved how starch, once rendered solu-
ble, went from one tissue to another, as much as to
accumulate again, as much as to bind in strong aggre-
gation and participate in this form in the formation of
cellular membranes in the tissue.
In 1823, J ohann Wolfgang Dbereiner (1780-1849)
obtained a spongy platinum material by calcinating
ammonium chloroplatinate
32
. This material was
shown to be able to absorb hydrogen at room condi-
tions and on heating up to ignite a stream of air di-
rected to it. Water was formed as a result without the
spongy mass changing its aspect or its weight, and
being capable of repeating the process after cooling.
In those days, when there was no simple way to pro-
duce fire, Dbereiners discovery led immediately to
its application, the hydroplatinic lamp, also called
briquet hydrogene (hydrogen lighter).
Platinum did not behave in this manner only when
made as a sponge; it did also when finely divided as
filings, wire, or turnings, as long as it was first heated
slightly. Many experiments led to think that this activ-
ity increased the more the platinum was divided; it
even increased more if before calcination the aqueous
solution of chloroplatinate was boiled with a little of
sodium carbonate and sugar. The chloroplatinate was
completely decomposed and the metal precipitated as
a black powder. This powder was much more active
than the sponge; it absorbed hydrogen rapidly and the
smallest particle led to the instantaneous ignition of a
mixture of hydrogen and air. Thnard then found that
black platinum decomposed hydrogen peroxide rap-
idly and with violence into oxygen and water, without
absorbing the gas releasing or losing its activity
33
. By
1900 this property of platinum was found also in other
metals (such as copper and iron), metallic oxides
(such as manganese dioxide), carbon, certain acids,
etc. The only difference with platinum was that these
additional materials had to be heated, sometimes to
red temperature
34
.
In his 1836 Annual Survey
35
, J ns J acob Berzelius
(1779-1848) summarized the findings of different
scientists on the formation of ether from alcohols; on
the enhanced conversion of starch to sugar by acids;
the hastening of gas combustion by platinum, the
stability of hydrogen peroxide in acid solution but its
decomposition in the presence of alkali and such
metals as manganese, silver, platinum, and gold; and
the observation that the oxidation of alcohol to acetic
EDUCATOR


237
acid was accomplished in the presence of finely
divided platinum. In a brilliant stroke, he was able to
understand that all these processes, although
seemingly different, had a common denominator,
which he called catalysis (either catalysis of inorganic
reactions by metals or of biological reactions by
enzymes). In the Annual Survey he wrote: In
inorganic nature when compounds arise through the
interaction of several substances, the available
combining units strive for a state of better satisfaction.
Thus, the substances endowed with strong affinities
combine readily on the one hand, while those weakly
endowed form combinations among themselves on
the other. The agent causing the conversion of
substances does not participate in the new compounds
formed but remains unchanged, thus operating by
means of an internal power, the nature of which is still
unknown, although it was in this way that it revealed
its existence. Thus, it is certain that substances, both
simple and compounds, in solid form as well as in
solution, have the property of exerting an effect on
compound bodies which is quite different from
ordinary affinity in that they promote the conversion
without necessarily participating in the process. This
is a new power to produce chemical activity
belonging to both inorganic and organic natures. It
will also make it easier for us to refer to it if it
possesses a name of its own I shall call it the catalytic
power of substances, and decomposition by means of
this power catalysis( from the Greek kata-,
"down" and lyein "loosen).

Mechanism of catalysis
When Sabatier commenced his investigations on
catalysis there were two theories of heterogeneous
catalysis, a physical and a chemical one. In 1833, af-
ter studying the data on the catalytic combination of
hydrogen and oxygen on the surface of platinum,
Faraday suggested a physical theory in which one or
more of the reacting gases were condensed by attrac-
tion on the surface of the metal. He wrote: The
course of events when platinum acts upon and com-
bines oxygen and hydrogen may be stated according
to these principles as follows. From the influences of
the circumstances mentioned, ie, the deficiency of
elastic power and the attraction of the metal for the
gases, the latter, when they are in association with the
former, are so condensed as to be brought within the
action of their mutual affinities at the existing tem-
perature, the deficiency of their elastic power not only
subjecting them more closely to the attractive influ-
ence of the metal, but also bringing them into more
favourable states for union by abstracting a part of
that power (upon which depends their elasticity)
which elsewhere in the mass is opposing their combi-
nation. The consequence of their combination is the
production of the vapour of water and an elevation of
temperature. But as the attraction of the platina for the
water formed is not greater than for the gases, if so
great (for the metal is scarcely hygrometric), the va-
pour is quickly diffused through the remaining gases.
The platina is not considered as causing combination
of any particles with itself but only associating them
closely around it and the compressed gases are as free
to move from the platina being replaced by other par-
ticles as a portion of dense air upon the surface of the
globe or at the bottom of a deep mine is free to move
by the slightest impulse into the upper and rarer parts
of the atmosphere.
Berzelius argued that the catalytic force acted on
the polarity of atoms through some phenomenon of
temperature elevation.
The physical theory was supported by the work of
J acques Duclaux (1877-1978) and Moissan on the
absorption of gases by finely divided metals
36,37
.
Wilhelm Ostwald (1853-1932; 1909 Nobel Prize
for Chemistry) and others had also assumed that cata-
lyzed gas reactions resulted from the absorption of
gases in the cavities of the porous metal, where com-
pression and local temperature elevation led to chemi-
cal combination. Ostwald believed that a catalyst did
not induce a reaction but rather accelerated it but not
with formation of intermediate compounds. He argued
it was necessary to prove that the succession of as-
sumed reactions required less time than the direct re-
action itself.
William Charles Henry (1774-1836) in 1824
38
and
August de la Rive (1801-1873) in 1828
39
proposed a
chemical theory where intermediate compounds, for
example, oxides of metals, were formed and decom-
posed.
Sabatier did not accept this purely physical view of
the function of the catalyst, remarking that if it was
true then charcoal should be almost a universal cata-
lyst, whereas it proved to be somewhat mediocre ex-
cept for the formation of carbonyl chloride
40
. While
finely divided metals were able to absorb substantial
quantities of gas, these absorptions were somewhat
specific, being characterized by a sort of selective
affinity. Not only that, some catalytic reactions were
extremely specific, for example, zinc oxide decom-
INDIAN J . CHEM. TECHNOL., MARCH 2005


238
posed formic acid into hydrogen and carbon dioxide,
but at the same temperature titania gave carbon mon-
oxide and water. The idea that absorption of gases
facilitated their liquefaction could not be true since
the easily absorbable hydrogen was very difficult to
liquefy. The physical theory was unable to explain the
development of high local pressure and temperature in
the cases where the catalyst was held in suspension,
and did not account for the specificity of catalysts and
the remarkable diversity of effects they produced, de-
pending on the particular metal or oxide used
1,40
.
Sabatier and his students observed that an extended
surface was not necessarily a synonym of catalytic
activity. For example, colloidal nickel, contrary to
palladium and nickel, was essentially inert. The activ-
ity of the catalyst depended particularly of the surface
structure; this was the reason why it was preferable to
use a chemical method of preparation instead of me-
chanical ones. Sabatier demonstrated that the manner
by which the reducible oxide was prepared played a
critical role, and searched which were the best deriva-
tives to prepare the reduced metal. He also showed
that these metallic catalysts were extremely fragile
and that they became stronger when using high reac-
tion temperatures. Higher temperatures led to an irre-
versible decrease of the catalytic activity; the activity
was not recovered if the operating temperature was
lowered
8
.
Sabatier then formulated a chemical theory of ca-
talysis involving the formation of unstable chemical
compounds as intermediate stages, which determined
the direction and rate of the reaction. He assumed that
in hydrogenation various nickel hydrides were in-
volved, whose composition depended on the activity
of the nickel. Carefully prepared nickel resulted in the
very active NiH
2
, which would operate on benzene,
while impure nickel or nickel prepared at too high
temperature gave an impoverished hydride, Ni
2
H
2
,
which is inactive with benzene, but works with the
ethylenic carbides or nitrate derivatives. Sabatier ar-
gued that the formation and decomposition of inter-
mediate compounds usually corresponds to a diminu-
tion of the Gibbs energy of the system. This reduction
is accomplished in several steps and this process is
frequently much easier than an immediate and direct
decrease of Gibbs energy, just as the use of a staircase
facilitates a descent
1
. He argued that while the pres-
ence of catalyst might indeed lower the temperature
required by a reaction, the catalysts greatest asset
was in reacting with a molecular gas in order to pro-
vide a free ion for a reaction which simply would not
occur otherwise. Thus, hydrogen peroxide solutions
decompose relatively slowly in the cold the same as
solutions of chromic acid do, but when the two solu-
tions are mixed there is a rapid decomposition with
brisk evolution of oxygen and appearance of an in-
tense blue colouration (reciprocal catalysis). The col-
our is due to the unstable combination
3H
2
O
2
.2H
2
CrO
4
, which can be isolated by shaking
with ether and evaporating the ether
1
.
Sabatier also addressed himself to the problem of
orientation and specificity of the catalyst and claimed
that they strongly supported the chemical theory. He
showed that different contact masses produced differ-
ent reactions: At 350C amyl alcohol in the presence
of copper yielded valeric aldehyde and hydrogen; at
the same temperature but in the presence of some tho-
ria as catalyst it yielded amylene and water. Chromic
oxide acted both in oxidation and in dehydrogenation
and dehydration reactions and heated alumina decom-
posed alcohol into ethylene and steam, while metallic
molybdenum and zinc oxide decomposed it into acet-
aldehyde and hydrogen. He attributed the orientation
of the reaction to the metallic or nonmetallic character
of the catalyst or, in other words, to the intervention
of different electrical contact forces. He understood
that this differentiation was not valid in every case.
He wrote: J ai trouv avec M Mailhe que les vapeurs
dacide formique en prsence doxyde de zinc
250C, donnent de lanhydride carbonique et de
lhydrogne, en presence doxyde titanique elles se
dtruisent exclusivement en eau et oxyde de carbone
Ici les deux oxides nont aucune dissemblance physi-
que et lintervention daffinit chimique spciale
sexerant la surface de ces catalyseurs est seule
capabe dexpliquer une inversion aussi complete du
phnomne (I have found with M Mailhe that va-
pours of formic acid in the presence of zinc oxide at
250C yield carbon dioxide and hydrogen, in the
presence of titania they decompose only into water
and carbon monoxide. Here, the two oxides do not
have any physical resemblance and the intervention of
a special chemical affinity that is exerted at the sur-
face of the catalyst is capable of explaining such a
complete inversion of the phenomenon)
8
.
Sabatier postulated the formation of different in-
termediate compounds, each with its own mode of
decomposition, and he also clearly established that
some organic reactions are reversible. In cases where
the intermediate compounds could not be isolated, he
EDUCATOR


239
assumed the formation of surface compounds, a phe-
nomenon, which he named fixation, thus linking the
physical, and the chemical theories of catalysis
41
. For
example, in the catalytic oxidation of organic com-
pounds with the aid or copper, or the decomposition
of carbon monoxide on nickel, the intermediaries,
copper oxide and nickel carbonyl, respectively, can be
isolated and identified. On his studies of the hydro-
genation of ethylene, Sabatier suggested the fixation
of hydrogen by the nickel as the intermediary com-
plex. In the case of acetylene, however, he remarked
that it was adsorbed more energetically than hydro-
gen, thus indicating the possibility of organometallic
compounds playing a role in heterogeneous cataly-
sis
42
. During his acceptance speech at Stockholm Sa-
batier said
43
: J admets que lhydrogne agit sur le
mtal en donnant trs rapidement sur sa surface une
combinaison Lhydrure ainsi engendr est facilement
et rapidement dissociable, et sil est mis en prsence
de matires capables dutiliser de lhydrogne, il le
leur cede, en rgnrant le mtal, qui recommence
indfiniment le mme effect La distinction que jai
faite entre plusieurs sortes deactivit du metal
conduirait admettre quil existe plusieurs stades de
combinaison (I admit that hydrogen acting on the
metal produces rapidly on its surface a combination.
The hydride thus generated is easily and rapidly dis-
sociated; put in contact with substances capable of
using hydrogen, gives it to them, regenerating the
metal and restarting indefinitely the process)
8
.
Sabatier summarized his views in respect to the
mechanism of catalytic action as follows
1,40
: As far
as I am concerned, this idea of temporary unstable
intermediate compounds has been the beacon light
that has guided all my works on catalysis; its light
may perhaps be dimmed by the glare of light as yet
unsuspected which will rise in the better explored
fields of chemical knowledge. Actually, such as it is,
in spite of its imperfections and gaps, the theory ap-
pears to us good because it is fertile and permits us in
a useful way to foresee reactions.
We must note that Sabatier was the first to demon-
strate, the reversibility of the reaction alco-
holaldehydehydrogen, which gave place to a large
number of thermodynamic and statistical investiga-
tions on the Gibbs energy changes of organic reac-
tions.
During the Second World War Irving Langmuirs
(1881-1957; 1952 Nobel Prize for Chemistry) pub-
lished a rival theory called theory of chemisorption,
according to which a gas adsorbed over a catalyst was
fixed thanks to its unsaturated valences yielding a
gas-metal compound of the type M
x
G
y
, where x is a
function of the mass of the catalyst and y varies ac-
cording to the specific surface and physical conditions
of pressure and temperature
44,45
. This theory was con-
trary to Sabatiers hypothesis of distinct, individual
intermediates and allowed more importance to physi-
cal conditions
19
. Although Langmuirs theory retained
the concept of fixation of the reagents on the surface
of the catalysts, it assigned a predominant importance
to the physical conditions that Sabatier had purpos-
edly ignored. For a time, Langmuirs theory of the
fixation of a monomolecular layer on the catalyst
gave it a certain advantage because it permitted to
address quantitatively the problem of heterogeneous
catalysis and played a considerable role in experimen-
tal studies
8
. Langmuirs theory became particularly
important because it permits a first quantitative analy-
sis of the possible mechanism of a reaction.

Poisoning
The catalysts sensitivity to poisons, discovered by
the work of Rudolph Knietsh (1854-1906) on cata-
lysts used for the synthesis of sulphur trioxide (was
shown to be a general phenomenon, which could be
used to control catalytic reactions Sabatier, when
comparing catalysts to ferments, described poisoning
in the following words: Comme les ferments or-
ganiss qui sont tus par des doses infinitsimales de
certains toxiques, le ferment minral quest le mtal
est tu par des traces de chlore, de brome, diode, de
soufre, darsenic, soit quelles lui viennent par
lhydrogne soit quelles lui soient apportes par la
substance qui doit subir lhydrogenationle nickel un
peu intoxiqu ne pourrait fournir quun premier hy-
drure, comparable celui du cuivre, et capable dagir
sur les groupes nitrs ou sur la double liason thyl-
nique; seul le nickel sain pourrait fournir un hydrure
capable dhydrogner le noyau aromatique (In the
same way that organized ferments are killed by infini-
tesimal amounts of certain toxins, the mineral ferment
which is the metal is killed by traces of chlorine, bro-
mine, iodine, sulphur, or arsenic that are carried by
the hydrogen or by the substance to be hydrogen-
atednickel, a little poisoned, can only provide a first
hydride, similar to that of copper and capable of act-
ing over the nitro groups or on the ethylenic double
bond, only nickel cannot provide a hydride able to
completely hydrogenate the aromatic ring)
1,8
.
Sabatier and Espil
46
made the interesting discovery
INDIAN J . CHEM. TECHNOL., MARCH 2005


240
that after being used to hydrogenate nitrobenzene,
nickel poisoned by chlorine recovers its ability to hy-
drogenate benzene
1
.
Discussion on the life and scientific career of Sa-
batier, in the following paras will give an overall view
of the background that led to this major contribution.

Life and career
Paul Sabatier (Fig. 1) was born on November 5,
1854, at Carcassonne, Southern France, one of the
seven children of Alexis Sabatier and Pauline Guil-
hem. He received his first education at the primary
school and the local Lyce in Carcassonne. In 1868,
he entered the Lyce at Toulouse and a year later
joined the Collge Saint-Marie. In J une 1872, after
receiving his diplomas of bachelier s sciences
(bachelor of sciences) and bachelier s letter (bache-
lor of humanities), he departed for Paris to prepare for
the entrance examinations to the Grand coles (cole
Polytechnique and cole Normale Suprieure). Al-
though he placed highly in the entrance competitions
for both coles, he chose the latter, where his brother
Thodore has preceded him
19,47
. At the cole Normale
he took the courses given by Henry Sainte-Claire De-
ville (1818-1881), Charles Friedel (1832-1899), J ean
Gaston Darboux (1842-1917), and Pierre Auguste
Bertin (1818-1884)
8
.
Three years later (1877), Sabatier received the li-
cense de physique and the license de mathmatiques
at the cole Normale and joined the local school at
Nmes as professor of physics. In 1878, he was rec-
ommended as normalien to the laboratory of Marcelin
Berthelot (1827-1907), then at the Collge de France.
At that time, Berthelot was the most outstanding
chemist of France and was well connected to the high
ranks of the academic and political establishment.
Sabatier took advantage of his stay at the Collge de
France to successfully prepare for his doctorate, re-
ceiving the degree of Docteur s Sciences (Doctor of
Sciences) in 1880 with a thesis on the thermochemis-
try of sulphur and metallic sulphides
48
.
The fact that Sabatier had been raised at home on a
religious and conservative atmosphere soon led to
strong divergences of opinion with Berthelot on po-
litical and philosophical grounds. This inflexible posi-
tion explains why Berthelot forced Sabatier to use in
his thesis the notation of equivalents (as seen in all the
tables), instead of the atomic one. Nevertheless, at
various points in his thesis Sabatier mentions that his
experiments confirm Berthelots principles or predic-
tions
8,1
.
These divergences affected profoundly Sabatiers
career In 1880, after receiving his doctorate Berthelot
led him to understand that he should look for a posi-
tion in the provinces. In France of that time this
statement was equivalent to academic exile. Berthelot
was known to punish in this harsh manner those who
criticized his theories and opposed his ideas. One of
the most famous scientists thus penalized was Pierre
Maurice Duhem (1861-1916)
49
. His choices to start an
academic career were now limited to three universi-
ties: Algiers, Bordeaux, or Lyon. Berthelot recom-
mended Sabatier for the position at Bordeaux, where
he stayed for one year as Matre de conferences in
physics. Eventually Sabatiers personality and bril-
liant scientific achievements overcame the ideological
barrier and on December 1905 he became Doyen
(dean) of the Faculty of Sciences at Toulouse, a posi-
tion he occupied for the next twenty-five years.
Sabatier remained faithful to Toulouse for all his
life, turning down many offers of respectful positions
elsewhere. In 1907, he was offered Henri Moissans
(1852-1907; 1906 Nobel Prize for Chemistry) chair at
the Sorbonne and that of Berthelot at the Collge de
France (ironies of life!). Although he realized that all
candidates for the Acadmie des Sciences were re-
quired to be residents of Paris, he nevertheless chose

Paul Sabatier (1854-1941)

EDUCATOR


241
to remain at Toulouse. He retired from his professor-
ship in 1930 after nearly fifty years of uninterrupted
service in the Faculty of Science.
In 1913, he became the first scientist elected to one
of six chairs newly created by the Acadmie for pro-
vincial members.
Sabatiers initial researches were in the field of in-
organic and physical chemistry, within the framework
of Berthelots laboratory. His thesis, which sought to
complete the study of sulphides, included accounts of
the preparation of various metal and nonmetal, espe-
cially alkali and alkaline-earth sulphides and polysul-
phides, with determinations of their heat of reaction
and solution. As described below, Sabatier ap-
proached the problem from a variety of possibilities.
In the 1879-1897 period, he performed analyses of
metallic and alkaline earth sulphides, chlorides,
chromates, and notably of copper compounds
7
, the
preparation of hydrogen disulphide by vacuum distil-
lation, the isolation of selenides of boron and silicon,
the definition of basic cupric salts containing four
copper atoms, and preparation of the deep blue nitro-
sodisulphonic acid and the basic mixed argentocupric
salts. He studied the partition of a base between two
acids, using the spectrophotometric change of colour-
ation of chromates and dichromates, as an indicator of
acidity
50,51
, and analyzed the velocity of transforma-
tion of metaphosphoric acid
52
. From 1896 to 1899, he
made some in-depth studies of the oxides of nitro-
gen
12,53-55
and of nitrosodisulphonic acid and its
salts
3,55-58
.
Sabatier himself has described how his interest in
the field of catalysis arose
12
. In 1890, after learning
that Ludwig Mond (1839-1909), Carl Langer, and
Friedrich Quincke had succeeded in preparing nickel
carbonyl
13
, a volatile compound, by the direct action
of carbon monoxide on finely divided nickel he de-
cided to investigate the possibility that other incom-
plete (unsaturated) gaseous molecules would behave
in the same manner, giving well-defined, stable, and
volatile products comparable to nickel carbonyl. In
collaboration with his doctoral student J ean Baptiste
Senderens (1856-1937) they succeeded in preparing
nitrated copper, Cu
2
NO
2
, by reacting NO
2
with re-
duced copper at room temperature
15
.
Sabatier and Senderens were about to try to fix
acetylene on several metals (copper, cobalt, iron, and
nickel) when they learned that Moissan and Franois
Charles Lon Moureu (1863-1929) had failed to
achieve it
16
. Sabatier and Senderens tried instead the
less violent reaction of ethylene and reduced nickel
and found that the reaction product was mainly ethane
with a little of hydrogen. Discovery of this hydro-
genation reaction opened a new world of chemical
synthesis, which was intensively researched by Sabat-
ier and his students. He promptly demonstrated the
general applicability of his method to the hydrogena-
tion of unsaturated and aromatic carbides, ketones,
aldehydes, phenols, nitriles, nitrate derivatives, carbon
monoxide and carbon dioxide, and liquid fats. He also
showed that certain metallic oxides, particularly man-
ganous oxide, behave analogously to metals in hydro-
genation and dehydrogenation, although at slower
rates; and that powdered oxides such as thoria, alu-
mina, and silica possess hydration and dehydration
properties. His work revealed also the general in-
crease in catalytic activity arising from the dispersal
of the active material on suitable supports.
Sabatiers discoveries lay at the root of most of the
giant chemical industries of today (petroleum, petro-
chemicals, chemical synthesis, synthetic fuels, fat hy-
drogenation, etc), nevertheless, like Claude-Louis
Berthollet (1748-1822) and Michael Faraday (1791-
1867) before him, he pursued science only and did not
seek the commercial benefits of his inventions, pat-
enting very few of them.
Sabatier passed away in Toulouse on August 1941,
at the age of 87.
The scientific work of Sabatier was very extensive;
in addition to a large number of speeches, reports, and
eight patents, he published over 250 scientific mem-
oirs, his famous book La Catalyse en Chimie Or-
ganique
1
(1913), as well as Leons lmentaires de
Chimie Agricole
2
(1890), and collaborated in major
works such as Edmond Frmys (1814-1894)
LEncyclopdie. Charles-Adolph Wrtzs (1817-
1884) Dictionnaire de Chimie, and Moissanss book
Chimie Minrale.
La Catalyse en Chimie Organique was first pub-
lished in 1913; this book on catalysis marks a mile-
stone in the evolution of modern chemistry and still
continues to be quoted extensively.

Honors and Positions
Sabatier received many honours for his contribu-
tion to science, industry, and the Nation. He became
Correspondent Member of the Acadmie and was
nominated to the Lgion d'Honneur. He was awarded
the degree of Doctor of Science, Honoris Causa, by
several foreign universities and elected member or
INDIAN J . CHEM. TECHNOL., MARCH 2005


242
honorary member of many foreign scientific societies.
In 1897, the Acadmie des Sciences awarded him the
Lacaze prize and in 1905 the J ecker prize, jointly with
Senderens. The Royal Society of London awarded
him the Davy Medal (1915) and the Royal Medal
(1918), the Royal Society of Arts the Albert Medal
(1926), and the Franklin Institute the Franklin Medal
(1933).
The maximum award came in 1912 when Sabatier
was awarded the Nobel Prize of Chemistry for his
method of hydrogenating organic compounds in the
presence of finely divided metals. He shared the prize
with Victor Grignard (1871-1935), who received it on
account of his discovery of the so-called Grignard
reagent.
Interesting enough, the road of both Sabatier and
Grignard to the Nobel Prize of Chemistry was deter-
mined by a twist of destiny. As mentioned before,
Sabatier went to become a chemist and not an engi-
neer because his acceptance to the cole Polytech-
nique was arrived several days after that to the cole
Normale Suprieure. In 1887, Grignard graduated
with honours the lyce at Cherbourg. At that time the
city of Paris offered scholarships to brilliant graduates
from the secondary schools in the provinces, to pre-
pare for the entrance examinations to one of her uni-
versities. The Cherbourg lyce had received a promise
that Grignard would be awarded one of those scholar-
ships in order to prepare for the entrance examina-
tions to the cole Normale Suprieure in Paris, to
study mathematics. Unfortunately, because of the ex-
penses involved in the preparation of the 1889 World
Exposition (that would see the inauguration of the
Eiffel Tower) no scholarships were offered at the time
of Grignards graduation from high school.
Whoever took the decisions that affected the ca-
reers of Sabatier and Grignard, could have hardly
guessed the tremendous impact they would have in
the development of modern organic chemistry.

Epilogue
Sabatier ended his speech at the Nobel Prize award
ceremony saying
43
: Theories cannot be indestructi-
ble. They are only the plough, which the ploughman
uses to draw his furrow and which he has every right
to discard for another one, of improved design, after
the harvest. To be this ploughman, to see my labours
result in the furtherance of scientific progress, was the
height of my ambition, and now the Swedish Acad-
emy of Sciences has come, at this harvest, to add the
most brilliant of crowns.


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